β-phenoxyethylamines and their use for the preparation of dyestuffs

ABSTRACT

The preparation is described of compounds of the structure ##STR1## in which the substituents have the meanings indicated in the description. The compounds, which are in part new, are used as intermediate products for dyestuffs.

This is a division of application Ser. No. 396,175, filed Aug. 21, 1989,now U.S. Pat. No. 5,041,629.

The present invention relates to β-phenoxyethylamines of the structure##STR2## wherein Z=NH₂ or NO₂,

M=H or an alkali metal cation, alkaline earth metal cation or ammoniumcation,

R=H or a C₁ -C₄ -alkyl, C₂ -C₄ alkenyl or C₂ -C₄ alkinyl radical each ofwhich is optionally substituted (in particular by OH, Cl, Br, CN, CO₂ H,CO₂ CH₃, CO₂ C₂ H₅, CONH₂, CON(CH₃)₂, SO₃ H, OSO₃ H and C₁ -C₄ -alkoxy)or a phenyl or benzyl radical each of which is optionally substituted(in particular by halogen, C₁ -C₄ -alkyl, CO₂ H or SO₃ H),

R¹ and R² =independently of one another H, C₁ -C₄ -alkyl, phenyl orbenzyl, it being also possible for R¹ -R² to be a constituent of acycloaliphatic radical,

X=SO₂ or CO and

Y=H or SO₃ H,

Y being SO₃ M if X=SO₂, and

Y being H if X=CO.

Preferred compounds (1) are those in which R¹ and R² =H and R=C₁ -C₄-alkyl, CH₂ CH₂ OH, CH₂ CO₂ H or CH₂ CH₂ OSO₃ H.

The invention also relates to a process for the preparation of thephenoxyethylamines (1) which is characterized in that2-halogeno-5-nitrobenzenesulphonamides or 2-halogen-5-nitrobenzamides ofthe structures (2) (which can be prepared by known methods from2-halogeno-5-nitrobenzenesulphonyl chloride or 2-halogeno-5-nitrobenzoylchloride, respectively, and the corresponding amines) ##STR3## whereinX, R, R¹ and R² have the meaning mentioned under formula (1)

are cyclized at 80° to 110° C. in the presence of bases, in particularalkali metal hydroxides or alkali metal carbonates, such as sodiumhydroxide solution, potassium hydroxide solution or sodium carbonate, togive 5,1,2-benzoxathiazepine 1,1-dioxides (X═SO₂) or1,4-benzoxaze-pin-5-ones (X═CO), respectively, of the formula (3)##STR4## these benzosultams or benzolactams, respectively, are thenreduced catalytically (for example hydrogen/catalyst), by means ofmetal/acid (for example iron/acetic acid) or by means of other reducingagents customary for aromatic nitro compounds to give amino compounds ofthe structure (4) ##STR5## and the latter are finally hydrolyzed withring opening. The hydrolysis of the benzosultams (X═SO₂) is preferablycarried out in oleum at 60°-120° C. and affords, as single substances,the claimed amidosulphonic acids of the structure (5). ##STR6## Thecorresponding alkali metal, alkaline earth metal or ammonium salts orbetaines are accessible by subsequent neutralization.

The hydrolysis of the benzolactams (X═CO) is most suitably effected bymeans of dilute mineral acids, such as dilute hydrochloric acid orsulphuric acid, at reaction temperatures of 80 -110° C., and affords, ifappropriate after neutralization, the claimed carboxy-substitutedβ-phenoxyethylamines of the structure (6) or hydrochlorides orhydrogensulphates thereof. ##STR7## The invention also relates to aprocess for the preparation of the phenoxyethylamines of the structure(1) which is characterized in that benzosultams or benzolactams of thestructure (3) are first hydrolyzed with ring-opening to give compoundsof the formula (7) or (8), respectively, ##STR8## benzosultams (3,X=SO₂) being preferably hydrolyzed at 60° to 120° C. in oleum to give(7) and benzolactams (3, X=CO) being preferably hydrolyzed at 90° to110° C. in dilute mineral acids, and the resulting nitro compounds (7)or (8) are finally reduced to give amino compounds of the structure (5)or (6), respectively. The reduction can be carried out catalytically(for example hydrogen/Raney nickel catalyst), by means of metal/acid orby means of other reducing agents customary for aromatic nitro groups.

The substitution or cyclization reaction leading to compounds of thestructure (3) is carried out on the model of DE-A 1,670,159 at above 80°C., most advantageously between 90° and 105° C., and if necessary underpressure. The reaction medium used is primarily water; it is alsopossible, however, to use an organic, water-miscible solvent, forexample alcohol, DMF or dimethyl sulphoxide, or a mixture of these withwater. It is preferable to carry out the reaction in water under refluxconditions. The auxiliary base is required to deprotonate the OH groupin (2) and to absorb the hydrogen halide H-Hal which is liberated in thecourse of the condensation reaction. The substitution reaction takesplace in an intramolecular manner giving single substances.

The use of 20% strength oleum at 75°-90° C. has proved particularlysuitable for the hydrolysis of the compounds (3, X=SO:) and (4, X=SO₂).

The invention also relates to new 7-amino-1,4-benzoxazepin-5-ones of thestructure (9) ##STR9## which are formed as intermediate products (4)having X=CO in the course of the process of preparation claimed, inparticular 7-amino-2,3-dihydro-(5H)-1,4-benzoxazepin-5-one,7-amino-4-methyl-2,3-dihydro-(5H)-1,4-benzoxazepin-5-one and7-amino-4-(2,-hydroxyethyl)-2,3-dihydro-(5H)-1,4-benzoxazepin-5-one.

The invention also relates to a process for the preparation ofintermediate products of the structure (3) in which X=SO₂ andR=optionally substituted C₁ -C₄ -alkyl, C₂ -C₄ alkenyl or C₂ -C₄alkinyl, which is characterized in that compounds of the structure (3)in which X=SO₂ and R=H are subjected to base-catalyzed alkylation withalkylating agents such as R-Hal or epoxides, such as, for example,chloroacetic acid or ethylene oxide, or with activated double bondsystems, such as, for example, acrylonitrile or acrylic acid esters. Thepreferred reaction medium in this case is water and the reactiontemperature is within the range from 50° to 110° C.

A process is also claimed for the preparation of β-phenoxyethylamines ofthe structure (10), such as are described, for example, in DOS (GermanPublished Specification) 3,635,312 ##STR10## in which Z=NO₂ or NH₂,which is characterized in that amidosulphonic acids of the structures(5) and (7) are hydrolyzed by means of dilute mineral acids, inparticular hydrochloric acid or sulphuric acid, under reflux conditionsor at elevated temperatures under pressure.

The use of the new, claimed compounds of the structures (1), (5), (6),(7), (8) and (9) is also claimed for the preparation of dyestuffs,especially of the compounds in which Z=NH₂, as diazo components in azodyestuff chemistry or as condensation components for activated quinones,such as chloranil, for the synthesis of triphendioxazine dyestuffs.

For the preparation of triphendioxazine dyestuffs compounds of theformula (1) or (10) in which Z=NH₂ are subjected to a condensationreaction in a known manner with 1,4-benzoquinones to give dyestuffprecursors of the formula (11) ##STR11## wherein T=Cl, Br, CO₂ CH₃, OCH₃or ##STR12## X=SO₂ or CO, Y=H or SO₃ M and M, R, R¹ and R² have themeaning mentioned under formula (1),

and a cyclization to give triphendioxazine dyestuffs of the formula##STR13## is then carried out, the X-OM radicals being in each case inone of the ortho-positions relative to the aminoethoxy radical. Thecyclization can be effected, for example, by methods such as aredescribed in German Offenlegungsschriften (German PublishedSpecifications) 2,122,262, 2,124,080, 2,302,382, 2,344,781, 2,503,611and 2,823,828 and in British Patent Specification 2,019,872. Dyestuffsof the formula (12) in which Y=SO₃ M can be hydrolyzed by means ofdilute mineral acids to give dyestuffs in which Y=H.

Dye bases of the formula (12) in which Y=H can also be reacted withreactive components of the structure Q-Hal (Q=a fiber-reactive radicaland Hal=Cl, Br or F) to give fiber-reactive triphendioxazine dyestuffs,some of which are known, of the formula (12) in which Y=Q wherein Q=afiber-reactive radical, in particular those belonging to the triazine orpyrimidine series (see DE-A 3,635,312).

The following are examples of typical dyestuffs: ##STR14##

Dyestuffs (12) in which Y=SO₃ H can also be prepared by subjectingactivated 1,4-benzoquinones to a condensation reaction with aminocompounds (4) by known methods (for example isopropanol/sodium acetate(60°-80° C.) to give dark olive dyestuff precursors of the structure(17) ##STR15## and then cyclizing the latter in oleum at 60°-120° C.,preferably at 75°-85° C., with simultaneous opening of the benzosultamor benzolactam ring system, to give triphendioxazines. The inventionrelates to this new process and also to the new red dyestuffs ordyestuff intermediate products of the structure (12) in which Y=SO₃ H.

Subjecting (17) to condensation in oleum at about 20°-40° C. givesdyestuffs of the following structure (18) ##STR16## which are also asubject of the invention.

The dyestuffs (12) in which Y=SO₃ H are particularly suitable for dyeingpaper and leather.

Dyestuffs (12) in which X=CO and Y=a fiber-reactive group are new andare also a subject of the invention. These dyestuffs are suitable fordying cotton.

Dyestuffs (18) containing groups which impart solubility in water arepreferentially suitable for dyeing paper and leather, while those whichare free from groups imparting solubility in water are suitable fordyeing synthetic materials or polyesters.

EXAMPLE 1

244 g of 8-nitro-3,4-dihydro-(2H)-5,1,2-benzoxathiazine 1,1-dioxide,which is accessible by an intramolecular condensation reaction from2-chloro-5-nitro-N-(2-hydroxyethyl)-benzenesulphonamide (DOS (GermanPublished Specification) 1,670,759), are suspended in 600 ml of methanoland are reduced in the presence of 3 g of freshly prepared Raney nickelas catalyst by injecting three times the equimolar amount of hydrogen inan autoclave at 50° C. When the reduction is complete, the catalyst isremoved from the hot reaction solution, from which the amino compoundcrystallizes out in fine flakes after cooling to 0° C. 205 g of8-amino-3,4-dihydro-(2H)-5,1,2-benzoxathiazepine 1,1-dioxide of theformula ##STR17## melting point 179° C. are obtained after filtering offwith suction and drying.

¹ H-NMR (D₆ -DMSO): δ=3.36 (2H,t); 3.91 (2H,t); 5.30 (NH₂,s); 6.61(1H,dd); 6.85 (1H,d); 6.94 (1H,d); 7.50 (NH,s) ppm.

The following amino compounds (Examples 2, 3 and 4) are accessible byreduction analogously:

EXAMPLE 2

8-Amino-2-methyl-3,4-dihydro-5,1,2-benzoxathiazepine 1,1-dioxide(melting point 148° C.) ##STR18##

¹ H-NMR (D₆ -DMSO): δ=2.62 (3H,s); 3.57 (2H,t); 3.97 (2H,t); 5.34(NH₂,s); 6.65 (1H,dd); 6.84-6.88 (2H,m) ppm.

EXAMPLE 3

8-Amino-2-(2-hydroxyethyl)-3,4-dihydro-5,1,2-benzoxathiazepine1,1-dioxide (melting point 141° C.) ##STR19##

¹ H-NMR (D₆ -DMSO) : δ=2.92 (2H,t); 3.53 (2H,m); 3.66 (2H,m); 3.99(2H,m); 4.82 (OH,t); 5.36 (NH₂,s); 6.67 (1H,dd); 6.84-6.92 (2H,m) ppm.

EXAMPLE 4

8-Amino-2-phenyl-3,4-dihydro-5,1,2-bonzoxathiazepine 1,1-dioxide(melting point 189° C.) ##STR20##

¹ H-NMR (d₆ -DMSO) : δ=4.02 (2H,m); 4.10 (2H,m); 5.40 (NH:,s); 6.74(1H,dd); 6.89 (1H,d); 6.98 (1H,d); 7.11 (2H,d); 7.22-7.37 (3H,m) ppm.

The 8-nitro-2-(2-hydroxyethyl)-3,4-dihyiro-5,1,2-benzoxathiazepine1,1-dioxide required for the preparation of Example 3 is accessible bythe following 2 methods of synthesis:

Route A)

324.5 g of N,N-bis(2-hydroxyethyl)-2-chloro-5-nitrobenzenesulphonamide,prepared from2-chloro-5-nitrobenzenesulphonyl chloride anddiethanolamine, are heated under reflux conditions in 1 1 of water with56 g of solid potassium hydroxide. After a reaction time of 1 hour thereaction mixture is cooled and the precipitated product is isolated. 262g of single-substance nitrobenzosultam are obtained (melting point 124°C).

Route B)

122 g of 8-nitro-3,4-dihydro-(2H)-5,1,2-benzoxathiazepine 1,1-dioxideare dissolved in 300 ml of water by adding 20 g of sodium hydroxide. Thesolution is heated to 60° C. with stirring and approximately 30-35 g ofethylene oxide are passed in slowly under a protective atmosphere of N₂.When the metered addition is complete stirring is continued for 2 hoursand the excess ethylene oxide is removed by passing in nitrogen. Thereaction mixture is neutralized and cooled to 20° C. Isolation of thecrystalline precipitate gives 129 g of an alkylation product whichproves to be identical with the8-nitro-2-(2-hydroxyethyl)-3,4-dihydro-5,1,2-benzoxathiazepine1,1-dioxide isolated by route A.

EXAMPLE 5

260 g of N-(2-hydroxyethyl)-N-methyl-2-chloro-5-nitrobenzamide, which isprepared from 2-chloro-5-nitrobenzoyl chloride and2-(methylamino)-ethanol, are heated to reflux temperature in 500 ml ofwater/500 ml of isopropanol. A solution of 65 g of potassium hydroxidein 250 ml of water is added dropwise in the course of one hour and themixture is maintained at reflux temperature for a further 3 hours. ThepH is lowered to 9, the reaction solution is cooled to 0° C. and thecrystalline precipitate is filtered off with suction and dried. 174 g of7-nitro-4-methyl -2,3-dihydro-1,4-benzoxazepin-5-one of melting point116° C. are obtained. ##STR21##

¹ H-NMR (D₆ -DMSO): δ=3.12 (3H,s); 3.71 (2H,m); 4.57 (2H,m); 7.17(1H,d); 8.22 (1H,dd); 8.61 (1H,d)ppm.

EXAMPLE 6

144.5 g of N,N-bis(2-hydroxyethyl)-2-chloro-5-nitrobenzamide in 500 mlof water containing 28 g of potassium hydroxide are heated for 2 hourswith reflux cooling. The mixture is cooled to 10° C. and theprecipitated, single-substance product is filtered off with suction anddried. 84 g of7-nitro-4-(2-hydroxyethyl)-2,3-dihydro-1,4-benzoxazepin-5-one of meltingpoint 151° C. are obtained. ##STR22##

¹ H-NMR (D₆)-DMSO); δ=3.67 (4H,m); 3.76 (2H,t); 4.58 (2H,t); 4.84(0H,t); 7.18 (1H,d); 8.23 (1H,dd); 8.66 (1H,d) ppm.

EXAMPLE 7

111 g of the nitro compound obtained under Example 5 are suspended in450 ml of methanol and are reduced, in the presence of 3 g of freshlyprepared Raney nickel as catalyst, by injecting three times theequimolar amount of hydrogen in an autoclave at 50° C. When thereduction has been carried out the catalyst is separated off from thewarm reaction solution. The solution is concentrated on a rotaryevaporator. 91 g of dry7-amino-4-methyl-2,3-dihydro-1,4-benzoxazepin-5-one of melting point165° C. are isolated. ##STR23##

¹ H-NMR (D₆ -DMSO): δ=3.04 (3H,s); 3.40 (2H,t); 4.13 (2H,t); 5.05(NH₂,s); 6.61(1H,dd); 6.68 (1H,d); 6.74 (1H,d) ppm.

EXAMPLE 8

The nitro compound obtained under Example 6 is reduced in a mannersimilar to that under item 7 to give7-amino-4-(2-hydroxyethyl)-2,3-dihydro-1,4-benzoxazepin-5-one of meltingpoint 138° C. ##STR24##

¹ H-NMR (D₆ -DMSO); δ=3.44 (2H,t); 3.53 (4H,m); 4.13 (2H,t); 4.80(0H,t); 4.99 (NH₂,s); 6.60 (1H,dd); 6.69 (1H,d); 6.72 (1H,d) ppm.

EXAMPLE 9

352 g (approximately 1.5 mol) of the amino compounds obtained in Example1 are introduced in portions into a stirred vessel containing 900 ml of20 % strength oleum. In the course of this, the temperature should notexceed 60° C. The mixture is then heated at 80° C. with stirring for 2hours. It is allowed to cool and is discharged onto a mixture of 500 mlof water and a total of 3.5 kg of ice.

When the temperature has reached 10°-15° C. the crystalline precipitateis filtered off with suction, rinsed with 200 ml of water and dried.This gives 537 g of amidosulphonic acid of the structure (probablybetaine structure) ##STR25## Determination of purity by means of sodiumnitrite solution gives a value of 38.5 g=0.1 mol, corresponding to ayield of 93 % of theory.

¹ H-NMR (D₂ O,NaOH): δ=3.36 (2H,t); 4.23 (2H,t); 6.91 (1H,dd); 6.98(1H,d); 7.22 (1H,d) ppm.

C,H,N-analysis: calc.: C: 30.76, H: 3.85, N: 8.976, O: 35.9, S: 20.51%found: C: 30.0, H: 3.9. N: 8.7, O: 35.4, S: 20.1%

EXAMPLE 10

If the amino compound from Example 2 is subjected to a process analogousto that described under Example 9, the result is a substitutedN-(β-phenoxyethyl)amidosulphonic acid of the structure ##STR26##

¹ N=NMR (D₂ O,NaOD): δ=2.84 (3H,s); 3.41 (2H,t); 4.25 (2H,t); 6.95(1H,dd); 7.03 (1H,d); 7.25 (1H,d) ppm.

EXAMPLE 11

300 g (1.2 mol) of the 8-nitro-3,4-dihydro-(2H)-5,1,2-benzoxathiazepine1,1-dioxide from Example 1, which is accessible by the method of DOS(German Published Specification) 1,670,759, are introduced in portionsinto a stirred vessel containing 800 ml of 20% strength oleum. In thecourse of this the temperature should not exceed 60° C. The mixture isthen heated at 80°-83° C. for 1 hour. Since the starting compound can nolonger be detected by chromatography, the reaction solution is cooled to20° C. and discharged onto an ice/water mixture. 48 g of sodiumhydroxide are introduced in portions and stirring is continued for 1hour. The crystalline precipitate is isolated and a small sample of itis dried. According to NMR data and analysis the hydrolysis product hasthe structure ##STR27##

¹ H-NMR (D₂₀,NaOD): δ=3.52 (2H,t); 4.48 (2H,t); 7.30 (1H,d); 8.35(1H,dd); 8.57 (1H,d) ppm.

EXAMPLE 12

The remainder of the material isolated, the moist paste, from Example 11is stirred into 800 ml of water and the pH of the mixture is adjusted to8 by means of concentrated sodium hydroxide solution, with externalcooling. After 5 g of Raney nickel have been added, hydrogen is injectedinto the autoclave at 25° C. A total of 3.2 mol of hydrogen are requiredfor the reduction. In the course of this the reaction temperature risesto 50° C. When the absorption of hydrogen is complete, the mixture iscooled and the pressure in the apparatus is released. The catalyst isremoved from the reaction solution by filtration. 200 ml of 48% strengthsulphuric acid are added to the solution, in the course of which thereduction product crystallizes out slowly. 340 g of an amino compoundwhich proves to be identical with the amidosulphonic acid of Example 9are obtained after isolation and drying. The content of amino compoundis 95.8% in respect of a molecular weight of 334 (mono-Na salt), that isto say the yield for the two reaction stages is 82% of theory.

EXAMPLE 13

250 g of the amidosulphonic acid derivative from Example 9 (81%strength) are boiled under reflux in 2.2 1 of 10 strength hydrochloricacid for about 6 hours until a sample no longer shows educt whenchromatographed. After being stirred under cold conditions over night,the product of the formula ##STR28## is precipitated in the form ofneedles, which are filtered off with suction, covered with cold 10%strength hydrochloric acid and dried. For analysis, it is preferable towash the product with acetone until it is free from hydrochloric acidand to dry it. This gives 149.8 g of the hydrochloride (86% of theory),which proves to be identical with a sample synthesized by a differentroute (as specified in DOS (German Published Specification) 3,635,312).

HCl calculated 13.59%: HCl found 13.63%.

EXAMPLE 14

46 g of the aminobenzolactam from Example 7 are heated under reflux in290 g of 60% strength sulphuric acid for approximately 36 hours. Thereaction solution is cooled and diluted with 250 ml of water. 160 g ofcalcium carbonate are introduced slowly until the pH has reached a valueof about 2. The temperature meanwhile is kept at 20°-25° C. by addingice. The precipitated calcium sulphate is removed and the resultingsolution is neutralized with dilute sodium hydroxide solution andconcentrated until crystallization begins. For further use, however, itis more advantageous after neutralization to react the solution of thecompound of the formula ##STR29## with suitable reactants, such as, forexample, chloranil, without further treatment.

EXAMPLE 15

21.8 g of the aminobenzolactam from Example 8 are boiled under reflux at110° C. in 66 ml of 20% strength hydrochloric acid for 8 hours until theeduct can no longer be detected by chromatography. Cooling gives awater-white solution which, after being concentrated in vacuo, suddenlydeposits a thick mash of crystals which, after being filtered off withsuction, can be dried in a circulating air drying cabinet. 30.3 g areisolated; according to argentometric determination of Cl, the productproves to be the bishydrochloride of5-amino-2-[2-(2-hydroxyethylamino)ethoxy]benzoic acid of the structure##STR30##

HCl calculated 23.3%: HCl found 23.4%.

¹ H-NMR(D₆ -DMSO): δ=3.16 (2H,m); 3.37 (2H,m); 3.68 (2H,t); 4.41 (2H,t);7.28 (1H,d); 7.55 (1H,dd); 9.13 (2H, broad s); 10.3-11.8 (approx. 2H)ppm.

EXAMPLE 16

44 g of 8-amino-3,4-dihydro-(2H)-5,1,2-benzoxathiazepine 1,1-dioxide(Example 1), 25.1 g of chloranil (=2,3,5,6-tetrachloro-1,4-benzoquinone)and 31 g of anhydrous sodium acetate are heated in 500 ml of isopropanolfor 5 hours with reflux cooling. The mixture is cooled and the productfiltered off with suction. The brown-olive material isolated is washedwith 50 ml of acetone and with three times 200 ml of water and is thendried. This gives 60.8 g of the bis-condensation product of thestructure ##STR31## 30 g of this sparingly soluble bis-condensationproduct are introduced in portions into 150 ml of 20% strength oleum at30°-40° C. The mixture is heated with stirring at 80°-85° C. for 3hours. After being cooled, the reaction solution is then discharged ontoice and the dark red precipitate is filtered off with suction. Afterisolation, the paste is neutralized by being stirred into 300 ml ofwater and the pH of the mixture is adjusted to 6.5 with dilute sodiumhydroxide solution. After 30 g of sodium chloride and 45 kg of potassiumchloride have been added, the mixture is stirred for 1 hour and theproduct is then again isolated by filtration. 26.1 g of a dark red-browndyestuff powder which has the structure ##STR32## are obtained afterdrying. The new product can be employed, for example, as an ink jetdyestuff and then gives a light-fast magenta (λmax.=540 nm (H₂ O)) onpaper.

We claim:
 1. A process for the preparation of a β-phenoxyethylamine of the formula ##STR33## wherein Z is NH₂ or NO₂,M is H or an alkali metal cation, alkaline earth metal cation or ammonium cation, R is H or a C₁ -C₄ -alkyl, C₂ -C₄ -alkenyl or C₂ -C₄ -alkynyl radical each of which is optionally substituted by OH, Cl, Br, CN, CO₂ H, CO₂ CH₃, CO₂ C₂ H₅, CONH₂, CON(CH₃)₂, SO₃ H, OSO₃ H or C₁ -C₄ -alkoxy, or a phenyl or benzyl radical each of which is optionally substituted by halogen, C₁ -C₄ -alkyl, CO₂ H or SO₃ H, R¹ and R² each independently is H, C₁ -C₄ -alkyl, phenyl or benzyl, or together they complete a cycloaliphatic ring, X is SO₂ or CO and Y is SO₃ M if X is SO₂, and Y is H if X is CO,comprising a) cyclizing a 2-halogen-5-nitrobenzenesulphonamide or 2-halogeno-5-nitrobenzamide of the formula ##STR34## wherein Hal is Cl, Br or F, at 80° to 110° C. in the presence of a base to give a 5,1,2-benzoxathiazepin 1,1-dioxide (X═SO₂) or a 1,4-benzoxazepin-5-one (X═CO), respectively, of the formula ##STR35## reducing the benzosultam or benzolactam to give an amino compound of the formula ##STR36## and hydrolyzing the amino compound with ring opening, or b) first hydrolyzing a benzosultam or benzolactam of the formula ##STR37## to give a compound of the formulae ##STR38## respectively, and then reducing the nitro group to an amino group.
 2. A process for the preparation of the phenoxyethylamines according to claim 1 in which Z═NH₂, wherein 2 halogeno-5-nitrobenzenesulphonamides or 2-halogeno-5-nitrobenzamides of the structures ##STR39## are cyclized at 80° to 110° C. in the presence of a base selected from the group consisting of sodium hydroxide solution, potassium hydroxide solution and sodium carbonate solution, to give 5,1,2-benzoxathiazepine 1,1-dioxides (X═SO₂) or 1,4-benzoxazepin-5-ones (X═CO), respectively, of the formula (3) ##STR40## which are then reduced catalytically or by means of metal/acid to amino compounds of the structure (4) ##STR41## and the latter are finally hydrolyzed with ring opening,
 3. A process for the preparation of the phenoxyethylamines according whereby benzosultams or benzolactams of the structure ##STR42## are first hydrolyzed to give compounds of the formulae ##STR43## respectively, and the nitro group is then reduced to the amino group. 